1. FIELD OF THE INVENTION
This invention relates to process and catalyst useful in the manufacture of ketones from olefins, and more particularly to lanthanide-containing catalysts useful in the vapor phase conversion of olefins to ketones.
2. DESCRIPTION OF THE PRIOR ART
U.S. Pat. No. 3,600,443 relates to a process for the oxidation of ethylene and propylene to the corresponding aldehyde or acid in the presence of oxygen and water vapor employing a vapor phase process in which the catalyst comprises a two-component heteropolyacid or oxide catalyst. The first component is an oxide of V, W or Mo, and the second component is an acid or oxide of B, Al, Si, Ti, Ge, Zr, Sn, Ce, P, As, Sb, Bi, S, Cr, Se, Te, Mn, Fe, Co or Ni. However, a significant selectivity loss to carbon dioxide and carbon monoxide was obtained in the preparation of acetone from propylene, and in the formation of acetaldehyde from ethylene. In the case of ethylene, increased conversion in a cerium-molybdenum-phosphomolybdic acid system was obtained at the expense of increased conversions to carbon oxides.
British Pat. No. 1,029,175 to Shell describes the vapor phase process in which olefin is reacted with oxygen at temperatures of less than 350.degree. C. in the presence of water vapor an a halogen, using a supported Group VIII noble metal catalyst containing either an iron, cobalt, nickel, or Group I or VII transition metal compound optionally together with an alkali metal compound. Catalyst activity is stated to be further enhanced by additional use of one or more transition metal compounds of Groups III-VI, such as the rare earth metal compounds, with mixtures of lanthanum and neodymium being exemplified. The oxidation of propylene is indicated to give acetone as the main reaction product. Such a halide-containing catalyst system has severe disadvantages due to the corrosivity of halide-containing systems. In addition, the process of British Pat. No. 1,029,175 provides undesirably high selectivities to carbon dioxide by-product.
R. A. Acuna et al., Anales de Quimica 1978, supp. 1, pages 17-23, report a study of the partial oxidation of propylene in the absence of an oxygen gas feed and in the presence of steam at atmospheric pressure and at temperatures of from 200.degree. to 400.degree. C. over mixtures of various supported metal oxides containing molybdenum oxide together with oxides of tin, iron, bismuth or antimony in bimetallic catalysts, as well as various supported trimetallic catalysts containing oxides of molybdenum and iron and, as a third metal oxide, either an oxide of tin, neodymium, antimony, cobalt, bismuth, niobium or copper. Comparisons of propylene oxidation over a trimetallic oxide catalyst containing molybdenum, iron and neodymium showed a large selectivity loss to carbon monoxide and carbon dioxide, the total selectivity to these oxides ranging from about 48 to 87 percent at temperatures of from 300.degree. to 380.degree. C.
Other early patents to the conversion of olefins to product mixtures containing ketones are U.S. Pat. No. 2,523,686 and British Pat. No. 876,024.
U.S. Pat. No. 2,523,686 to W. F. Engel of Shell employs oxide catalysts containing (1) an oxide of a metal of Groups II, III, IV, or VI of the Periodic Table and (2) a metal or partially reduced oxide of a metal of Group IB, Group VII or Group VIII of the Periodic Table, and prepares saturated open-ended ketones from olefins of at least three carbon atoms per molecule in a vapor phase process in the presence of steam and under defined conditions. Dutch Pat. No. 59,179, also to W. F. Engel, relates to the similar catalyst systems. British Pat. No. 876,024 converts olefins into the corresponding aldehydes and ketones by passing a mixture of the olefin and oxygen, optionally with steam, over catalysts containing metal compounds whose cations and metals of a transition metal of the fifth to eighth group or first sub-group of the Periodic System and whose anions are derived from strong acids. Exemplified strong acid salts are those containing halide (Cl, Br), NO.sub.3.sup.- and PO.sub.4.sup.=.